CN117181002B - Seawater desalination membrane and preparation method thereof - Google Patents

Seawater desalination membrane and preparation method thereof Download PDF

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CN117181002B
CN117181002B CN202311449171.8A CN202311449171A CN117181002B CN 117181002 B CN117181002 B CN 117181002B CN 202311449171 A CN202311449171 A CN 202311449171A CN 117181002 B CN117181002 B CN 117181002B
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chloride
membrane
water
component
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CN117181002A (en
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齐萨仁
曾浩浩
石楚道
何亮
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Hunan Keensen Technology Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

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Abstract

The invention relates to the technical field of membrane separation, in particular to a seawater desalination membrane and a preparation method thereof. The preparation method comprises the following steps: a) Coating an aqueous phase solution on the polysulfone supporting layer, then coating an oil phase solution, and drying to obtain a nascent reverse osmosis membrane; b) Sequentially immersing the nascent reverse osmosis membrane into a filling solution, a repairing solution and a glycerol solution, and drying to obtain a sea water desalination membrane; the filling solution comprises isopropanol, ethyl acetate, water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid; the repair solution comprises a component a, water and a component b; the component a comprises aliphatic dialdehyde or epoxy compound; the component b comprises tannic acid, nitric acid or hydrochloric acid; the temperature of the glycerol solution is 60-90 ℃. The seawater desalination membrane prepared by the invention has the advantages of better desalination rate and boron removal rate, better pollution resistance and longer service life.

Description

Seawater desalination membrane and preparation method thereof
Technical Field
The invention relates to the technical field of membrane separation, in particular to a seawater desalination membrane and a preparation method thereof.
Background
At present, a sea water desalination reverse osmosis membrane is generally prepared by adopting an interfacial polymerization method, belongs to a composite membrane, is generally of a 3-layer structure, and sequentially comprises a non-woven fabric layer, a polysulfone layer and a polyamide layer from bottom to top. The conventional preparation method comprises the following steps: casting the membrane on a non-woven fabric layer, preparing a polysulfone base membrane through a phase inversion method, immersing the polysulfone base membrane into an aqueous phase solution containing amine monomers and other additives, taking out, removing redundant solution through a vacuum pump, an air knife and the like, pouring an oil phase solution containing acyl chloride monomers and other additives on the surface of the membrane, performing interfacial polymerization reaction, removing redundant oil phase solution through an oven heating mode, and performing post-treatment processes such as rinsing and the like to obtain the complete sea water desalination reverse osmosis membrane.
However, the seawater desalination reverse osmosis membrane prepared by the conventional method has the following disadvantages:
1) The desalination rate of the seawater desalination reverse osmosis membrane is between 99.0% and 99.8%, and the application is limited due to the low desalination rate;
2) The boron removal rate of the seawater desalination reverse osmosis membrane is 70% -90%, and the boron removal requirement cannot be met;
3) The seawater desalination reverse osmosis membrane is easy to cause membrane pollution when treating the complex quality of seawater.
The prior improved technology generally adopts the following steps of: 1. the auxiliary agent and the nano material are added in the interfacial polymerization reaction process, so that the desalination rate and the boron removal rate of the membrane are improved; 2. and (3) physically coating polyvinyl alcohol (PVA) on the surface of the polyamide layer or further carrying out PVA crosslinking grafting on the surface of the membrane, so that the anti-pollution capability of the membrane is improved.
Although the introduction of the nano material can improve the separation performance and the water permeability of the membrane, the nano material has the defects of high price, difficult acquisition, agglomeration and the like, and cannot be suitable for industrial mass production. The PVA is coated on the surface of the membrane, so that the purpose of protecting the separation layer on the surface of the membrane can be achieved, the anti-pollution capability and the service life of the membrane are improved, however, in the long-time operation process, the PVA coated on the surface is easily washed away, the protection effect of the PVA is further lost, the effect of surface cross-linking grafting PVA is limited, the cross-linking effect is not obvious, and the PVA on the surface of the membrane is still easily lost in the long-time operation process.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a seawater desalination membrane and a preparation method thereof, wherein the seawater desalination membrane prepared by the invention has the advantages of better desalination rate and boron removal rate, better pollution resistance and longer service life.
The invention provides a preparation method of a seawater desalination membrane, which comprises the following steps:
a) Coating an aqueous phase solution on the polysulfone supporting layer, then coating an oil phase solution, and drying to obtain a nascent reverse osmosis membrane;
b) Sequentially immersing the nascent reverse osmosis membrane into a filling solution, a repairing solution and a glycerol solution, and drying to obtain a sea water desalination membrane;
the filling solution comprises isopropanol, ethyl acetate, water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid;
the repair solution comprises a component a, water and a component b; the component a comprises aliphatic dialdehyde or epoxy compound; the component b comprises tannic acid, nitric acid or hydrochloric acid;
the temperature of the glycerol solution is 60-90 ℃.
Preferably, in the step B), in the filling solution, the mass ratio of isopropanol, ethyl acetate, water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid is 60-80: 0.1-3: 10-30: 0.5-6: 1-4.
Preferably, in step B), the aliphatic dialdehydes include at least one of glyoxal, glutaraldehyde, suberaldehyde, 3-oxoglutaraldehyde, and thiodiglycol aldehyde;
the epoxy compound includes at least one of glycidol, diglycidyl ether, glycidyl butyl ether, polyglycidyl ether, epoxy fluoroether, triethylene glycol, butanediol diglycidyl ether, and diglycidyl terephthalate.
Preferably, in the step B), the mass ratio of the component a to the water to the component B is 1-10: 85-98.9: 0.1 to 5.
Preferably, in the step B), the mass concentration of the glycerol solution is 2% -10%.
Preferably, in the step B), the temperature of immersing the nascent reverse osmosis membrane in the filling solution is 25 ℃ and the time is 2-5 min;
immersing the repairing solution at 25 ℃ for 2-5 min;
the temperature of immersing in the glycerol solution is 60-90 ℃ and the time is 2-5 min.
Preferably, in step a), the aqueous solution comprises an amine monomer, a surfactant, a second organic solvent and water;
the amine monomer comprises at least one of p-phenylenediamine, m-phenylenediamine and 3, 5-diaminobenzoic acid, ethylenediamine, propylenediamine, butylenediamine, pentylene diamine, N- (2-hydroxyethyl) ethylenediamine, hexamethylenediamine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, piperazine and 4-aminomethylpiperazine;
the surfactant comprises at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and sodium stearate;
the second organic solvent comprises N-methyl pyrrolidone;
the mass ratio of the amine monomer to the surfactant to the second organic solvent to the water is 0.5-4: 0.01 to 0.5: 0.5-5: 90.5-98.5;
the temperature of the aqueous phase solution is 10-80 ℃.
Preferably, in step a), the oil phase solution comprises an acid chloride monomer and a third organic solvent;
the acyl chloride monomer comprises at least one of phthaloyl chloride, isophthaloyl chloride, biphenylyl dichloride, phthaloyl chloride, trimesoyl chloride, succinyl chloride, ding Sanxian chloride, glutaryl chloride, hexanedioyl chloride, sebacoyl chloride, cyclopropanetriacyl chloride, cyclobutanediacyl chloride, cyclobutanetetracyl chloride, cyclopentanedioyl chloride, cyclopentanetriacyl chloride, cyclopentanetetraacyl chloride, cyclohexanediacyl chloride, cyclohexanetetraacyl chloride, tetrahydrofuranodiacyl chloride and tetrahydrofurantetraacyl chloride;
the third organic solvent is Isopar G;
the mass ratio of the acyl chloride monomer to the third organic solvent is 0.05-0.5: 99.5-99.95;
the coating amount of the oil phase solution is 5-1250 mg/m 2 ；
The temperature of the oil phase solution is 10-80 ℃.
Preferably, in step a), after the oil phase solution is applied, the method further comprises:
and (5) after standing for 0.2-180 s, removing the redundant oil phase solution.
The invention also provides a sea water desalination membrane prepared by the preparation method.
The invention provides a preparation method of a seawater desalination membrane, which comprises the following steps: a) Coating an aqueous phase solution on the polysulfone supporting layer, then coating an oil phase solution, and drying to obtain a nascent reverse osmosis membrane; b) Sequentially immersing the nascent reverse osmosis membrane into a filling solution, a repairing solution and a glycerol solution, and drying to obtain a sea water desalination membrane; the filling solution comprises isopropanol, ethyl acetate, water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid; the repair solution comprises a component a, water and a component b; the component a comprises aliphatic dialdehyde or epoxy compound; the component b comprises tannic acid, nitric acid or hydrochloric acid; the temperature of the glycerol solution is 60-90 ℃.
Currently, the prior art uses a coating of polyvinyl alcohol on the surface of a polyamide separation layer or a cross-linking grafting of polyvinyl alcohol on the surface of a polyamide separation layer. The invention fills the polyvinyl alcohol into the polyamide layer, and simultaneously, under the action of the repairing agent (comprising repairing solution and glycerol solution), the crosslinking of amide molecular chains and the polyvinyl alcohol and the crosslinking between polyamide molecular chains are carried out in the polyamide layer, so that the crosslinking degree is high, and the defect of aggregation holes of the polyamide separating layer is repaired, in addition, as the 1, 5-naphthalene disulfonic acid is hybridized and filled in the polyamide separating layer, the steric hindrance of the polyamide separating layer and the acting force between boric acid molecules are increased, the diffusion of the boric acid molecules in the membrane is hindered, the desalination rate and the boron removal rate of a seawater membrane are improved, and meanwhile, as the polyvinyl alcohol is filled into the polyamide molecular chains, the polyvinyl alcohol is not easy to wash and separate from the surface of the reverse osmosis membrane, and the anti-pollution capability and the service life of the membrane are improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a seawater desalination membrane, which comprises the following steps:
a) Coating an aqueous phase solution on the polysulfone supporting layer, then coating an oil phase solution, and drying to obtain a nascent reverse osmosis membrane;
b) Sequentially immersing the nascent reverse osmosis membrane into a filling solution, a repairing solution and a glycerol solution, and drying to obtain a sea water desalination membrane;
the filling solution comprises isopropanol, ethyl acetate, water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid;
the repair solution comprises a component a, water and a component b; the component a comprises aliphatic dialdehyde or epoxy compound; the component b comprises tannic acid, nitric acid or hydrochloric acid;
the temperature of the glycerol solution is 60-90 ℃.
In step A):
and (3) coating an aqueous phase solution on the polysulfone supporting layer, then coating an oil phase solution, and drying to obtain the nascent reverse osmosis membrane.
In certain embodiments of the present invention, the method of preparing the polysulfone support layer comprises the steps of:
a1 Dissolving polysulfone in a first organic solvent at 60-80 ℃, and uniformly mixing the polysulfone with a pore-forming agent at 60-80 ℃ to obtain a homogeneous solution;
a2 And (3) after the homogeneous solution is defoamed, casting the solution onto non-woven fabrics, and curing the solution to obtain the polysulfone support layer.
In step A1):
the first organic solvent comprises one or two of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
The pore-forming agent comprises one or two of polyvinylpyrrolidone and polyethylene glycol; the molecular weight range of polyvinylpyrrolidone is 24000-1300000, and the molecular weight range of polyethylene glycol is 6000-20000. In certain embodiments of the invention, the polyvinylpyrrolidone (PVP) is PVP k30; the polyethylene glycol (PEG) is PEG800 or PEG1000.
In the homogeneous solution, the mass content of polysulfone is 12% -25%, the mass content of the first organic solvent is 70% -88%, and the mass content of the pore-foaming agent is 0% -5%. In certain embodiments of the present invention, the homogenous solution has a polysulfone content of 15% by mass, the first organic solvent content of 84.8% by mass, and the porogen content of 0.2% by mass.
In step A2):
the defoaming is static defoaming, and the time is 12-36 hours.
The curing method comprises the following steps: soaking in deionized water.
After the curing, the method further comprises the following steps: washing with deionized water and drying.
In certain embodiments of the present invention, the aqueous solution includes an amine monomer, a surfactant, a second organic solvent, and water.
The amine monomer includes at least one of aromatic amine and aliphatic amine. The aromatic amine comprises at least one of p-phenylenediamine, m-phenylenediamine and 3, 5-diaminobenzoic acid; the aliphatic amine comprises at least one of ethylenediamine, propylenediamine, butylenediamine, pentyenediamine, N- (2-hydroxyethyl) ethylenediamine, hexamethylenediamine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, piperazine and 4-aminomethylpiperazine.
The surfactant includes at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, and sodium stearate.
The second organic solvent comprises N-methylpyrrolidone.
The mass ratio of the amine monomer to the surfactant to the second organic solvent to the water is 0.5-4: 0.01 to 0.5: 0.5-5: 90.5 to 98.5, such as 3:0.3:2:94.7.
in certain embodiments of the invention, the aqueous solution further comprises a pH adjuster, such as sodium hydroxide. The pH value of the aqueous phase solution is 7.5-8.0.
The aqueous phase solution is prepared by uniformly mixing raw materials comprising amine monomers, a surfactant, a second organic solvent and water. In certain embodiments, the feedstock further comprises a pH adjustor.
The water is deionized water.
In some embodiments of the invention, the aqueous solution has a temperature of 10 to 80 ℃, preferably 15 to 60 ℃, such as 25 ℃.
In certain embodiments of the present invention, after coating the aqueous phase solution on the polysulfone support layer, further comprising:
and removing the excessive aqueous phase solution on the polysulfone support layer, and drying.
The drying comprises the following steps: and (3) placing the obtained base film in a closed space with the temperature of 20-30 ℃ and the relative humidity of 50-80% for drying. And the drying time is 1-5 min.
In certain embodiments of the invention, the oil phase solution comprises an acid chloride monomer and a third organic solvent.
The acyl chloride monomer comprises at least one of aromatic acyl chloride and fatty acyl chloride. The aromatic acyl chloride comprises at least one of phthaloyl chloride, isophthaloyl chloride, biphenyl diacid chloride, benzene disulfonyl chloride and trimesoyl chloride; the fatty acyl chloride comprises at least one of succinyl chloride, ding Sanxian chloride, glutaryl chloride, valeryl chloride, adipoyl chloride, hexatriacyl chloride, sebacoyl chloride, cyclopropane triacyl chloride, cyclobutane diacyl chloride, cyclopentane triacyl chloride, cyclopentane tetraacyl chloride, cyclohexane diacyl chloride, cyclohexane triacyl chloride, cyclohexane tetraacyl chloride, tetrahydrofuran diacyl chloride and tetrahydrofuran tetraacyl chloride.
The third organic solvent is one or more of aliphatic hydrocarbon containing 4-10 carbon atoms, cycloaliphatic hydrocarbon containing 4-10 carbon atoms and aromatic hydrocarbon containing 4-10 carbon atoms. Specifically Isopar G.
The mass ratio of the acyl chloride monomer to the third organic solvent is 0.05-0.5: 99.5 to 99.95, such as 0.3:99.7.
the oil phase solution is obtained by uniformly mixing raw materials comprising an acyl chloride monomer and a third organic solvent.
In some embodiments of the invention, the oil phase solution has a coating amount of 5-1250 mg/m 2 Specifically 50-500 mg/m 2 。
In some embodiments of the invention, the temperature of the oil phase solution is 10 to 80 ℃, preferably 35 to 70 ℃, such as 50 ℃.
In certain embodiments of the invention, the oil phase solution is applied in an excess amount.
In certain embodiments of the present invention, after applying the oil phase solution, further comprising:
and (5) after standing for 0.2-180 s, removing the redundant oil phase solution. In some embodiments, the rest is for 0.5 to 60 seconds. The removal of the excess oil phase solution is specifically: the excess oil phase solution was decanted and drained.
In some embodiments of the present invention, the temperature of the drying is 60-100 ℃ and the time is 3-6 min.
In step B):
sequentially immersing the nascent reverse osmosis membrane into a filling solution, a repairing solution and a glycerol solution, and drying to obtain a sea water desalination membrane;
the filling solution comprises isopropanol, ethyl acetate, water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid;
the repair solution comprises a component a, water and a component b; the component a comprises aliphatic dialdehyde or epoxy compound; the component b comprises tannic acid, nitric acid or hydrochloric acid;
the temperature of the glycerol solution is 60-90 ℃; in some embodiments, 70-90 ℃.
In some embodiments of the present invention, in the filling solution, the mass ratio of isopropanol, ethyl acetate, water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid is 60-80: 0.1-3: 10-30: 0.5-6: 1-4; such as 70:2:22:4: 2. 70:2:19:6: 3. 70:2:25:2:1. the water is deionized water.
The filling solution is prepared by uniformly mixing raw materials including isopropanol, ethyl acetate, water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid.
In certain embodiments of the present invention, the aliphatic dialdehyde comprises at least one of glyoxal, glutaraldehyde, suberaldehyde, 3-oxoglutaraldehyde, and thiodiglycollyde; the epoxy compound includes at least one of glycidol, diglycidyl ether, glycidyl butyl ether, polyglycidyl ether, epoxy fluoroether, triethylene glycol, butanediol diglycidyl ether, and diglycidyl terephthalate.
In some embodiments of the present invention, the mass ratio of the component a, the water and the component b is 1 to 10: 85-98.9: 0.1-5; such as 3:96.7:0.3, 3:96:1.
in the repair solution, the water is deionized water.
The repairing solution is prepared by uniformly mixing raw materials comprising water, a component a and a component b.
In some embodiments of the invention, the mass concentration of the glycerol solution is 2% -10%. The solvent of the glycerol solution is deionized water.
In certain embodiments of the present invention, before immersing the nascent reverse osmosis membrane in the fill solution in sequence, further comprising: after rinsing with RO water, the surface RO water is drained. The flushing time is 2-4 min.
In some embodiments of the present invention, the temperature of the nascent reverse osmosis membrane immersed in the filling solution is normal temperature (25 ℃) for 2-5 min, specifically 3 min. The temperature of immersing in the repair solution is normal temperature (25 ℃) for 2-5 min, specifically 3 min. The temperature of immersion in the glycerol solution is 60-90 ℃, in some embodiments 70-90 ℃; specifically 80 ℃; the time is 2-5 min, specifically 5 min. Draining is also included after each immersion is completed.
In some embodiments of the present invention, the temperature of the drying is 60-90 ℃ and the time is 4-6 min.
The invention also provides a sea water desalination membrane prepared by the preparation method.
According to the invention, a filling-repairing technology is adopted for aggregation holes among molecular chains, the winding degree among polyamide molecular chains is reduced under the condition of blending solution of isopropanol and ethyl acetate, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid are smoothly filled into the aggregation holes under the condition that the aggregation holes among the molecular chains are further opened, active crosslinking substances synchronously enter the aggregation holes, internal crosslinking is carried out among the polyamide molecular chains and between the polyamide molecular chains and the polyvinyl alcohol, and then the previously opened molecular chains and the aggregation holes filled with the polyvinyl alcohol and the 1, 5-naphthalene disulfonic acid are further folded under the action of high-temperature hot water. The seawater desalination reverse osmosis membrane with the hybridized filling separation layer is obtained, and the desalination rate, the boron removal rate and the pollution resistance of the membrane are further improved.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to describe in detail a seawater desalination membrane and a preparation method thereof, but should not be construed as limiting the scope of the present invention.
The reagents used in the following examples and comparative examples are all commercially available.
In the examples, preparation of polysulfone support layer:
dissolving polysulfone in N, N-dimethylformamide at 70 ℃, and then uniformly mixing the polysulfone with polyvinylpyrrolidone (PVP k 30) at 70 ℃ to obtain a homogeneous solution;
in the homogeneous phase solution, the mass content of polysulfone is 15%, the mass content of the first organic solvent is 84.8%, and the mass content of the pore-forming agent is 0.2%;
and standing the homogeneous solution for deaeration of 20 h, casting the solution onto non-woven fabrics, immersing the solution in deionized water, converting the solution into a solid film, cleaning the film with deionized water, and drying the film to obtain the polysulfone support layer.
Example 1
1) Preparing an aqueous phase solution:
30g of m-phenylenediamine, 3g of sodium dodecyl benzene sulfonate and 20g N-methyl pyrrolidone are added and dissolved in 947g of deionized water, and sodium hydroxide is adopted to adjust the pH value to 7.5-8.0, so that an aqueous phase solution is obtained.
2) Preparing an oil phase solution:
3G of trimesoyl chloride was dissolved in 997G of Isopar G and mixed to obtain an oil phase solution.
3) Preparing a filling solution:
isopropanol, ethyl acetate, deionized water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid are mixed according to the mass ratio of 70:2:22:4:2, uniformly mixing to obtain a filling solution.
4) Preparing a repairing solution:
adding suberaldehyde into deionized water, stirring uniformly, adding hydrochloric acid, and mixing uniformly to obtain a repairing solution; the mass ratio of the suberaldehyde to the deionized water to the hydrochloric acid is 3:96.7:0.3.
5) Preparing a glycerol solution:
and uniformly mixing glycerol and deionized water, and heating to 80 ℃ to obtain a glycerol solution with the mass concentration of 8%.
6) Preparation of a seawater desalination membrane:
6-1) coating aqueous phase solution at 25 ℃ on the polysulfone supporting layer, removing excessive aqueous phase solution on the surface of the coated polysulfone supporting layer, and then placing the obtained polysulfone supporting layer in a closed space at 30 ℃ and with relative humidity of 60% for drying for 1 min. Then, coating excessive oil phase solution at 50 ℃ on the obtained polysulfone support layer, standing for 30 seconds, pouring out and draining the excessive oil phase solution, and drying in an oven at 80 ℃ for 4 minutes to obtain the nascent reverse osmosis membrane.
6-2) washing the nascent reverse osmosis membrane with RO water for 3min, draining the RO water on the surface, immersing in a filling solution for 3min, taking out and draining, immersing in a repairing solution for 3min, taking out and draining, immersing in a glycerol solution at 80 ℃ for 5 min, taking out and draining, and drying at 60 ℃ for 5 min to obtain the sea water desalination membrane.
Example 2
The difference from example 1 is that:
in step 3), a filling solution is prepared:
isopropanol, ethyl acetate, deionized water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid are mixed according to the mass ratio of 70:2:19:6:3, uniformly mixing to obtain a filling solution.
Example 3
The difference from example 1 is that:
in step 3), a filling solution is prepared:
isopropanol, ethyl acetate, deionized water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid are mixed according to the mass ratio of 70:2:25:2:1, mixing evenly to obtain a filling solution.
Example 4
The difference from example 1 is that:
in step 4), preparing a repair solution:
adding butanediol diglycidyl ether into deionized water, uniformly stirring, adding tannic acid, and uniformly mixing to obtain a repairing solution; the mass ratio of the butanediol diglycidyl ether to the deionized water to the tannic acid is 3:96:1.
example 5
The difference from example 1 is that:
in step 4), preparing a repair solution:
adding triethylene glycol into deionized water, stirring uniformly, adding nitric acid, and mixing uniformly to obtain a repairing solution; the mass ratio of the triethylene glycol to the deionized water to the nitric acid is 3:96:1.
comparative example 1
1) Preparing an aqueous phase solution:
30g of m-phenylenediamine, 3g of sodium dodecyl benzene sulfonate and 20g N-methyl pyrrolidone are added into 947g of deionized water, and the pH value is regulated to 7.5-8.0 by adopting sodium hydroxide, so as to obtain aqueous phase solution.
2) Preparing an oil phase solution:
3G of trimesoyl chloride was dissolved in 997G of Isopar G and mixed to obtain an oil phase solution.
3) Preparation of a seawater desalination membrane:
and (3) after coating the aqueous phase solution on the polysulfone support layer, removing excessive aqueous phase solution on the surface of the coated polysulfone support layer, and then placing the obtained polysulfone support layer in a closed space with the temperature of 30 ℃ and the relative humidity of 60% for drying for 1 min. Then, coating excessive oil phase solution at 50 ℃ on the obtained polysulfone support layer, standing for 30 seconds, pouring out and draining the excessive oil phase solution, and drying in an oven at 80 ℃ for 4 minutes to obtain the nascent reverse osmosis membrane.
Comparative example 2
The difference from example 3 is that:
in step 3), the filling solution is formulated without isopropanol.
Comparative example 3
The difference from example 3 is that:
in step 3), the filling solution is formulated without polyvinyl alcohol.
Comparative example 4
The difference from example 3 is that:
in step 3), the filling solution is prepared without ethyl acetate.
Comparative example 5
The difference from example 3 is that:
in step 3), the 1, 5-naphthalene disulfonic acid is not contained in the prepared filling solution.
Comparative example 6
The difference from example 3 is that:
in step 4), the prepared repair solution does not contain octanedioldehyde.
Comparative example 7
The difference from example 3 is that:
in step 4), the prepared repair solution does not contain tannic acid.
Performance testing was performed on the seawater desalination membranes prepared in examples 1 to 5 and comparative examples 1 to 7:
1) The membrane flux, desalination rate and boron removal rate of the obtained seawater desalination membrane are tested under the conditions of 32000ppm of sodium chloride and 5ppm of boron as test solutions, the external pressure of 5.51MPa, the temperature of the aqueous solution of 25 ℃ and the pH of 7.0-8, and the results are shown in Table 1.
TABLE 1 Membrane flux, desalination and boron removal rates of seawater desalination membranes
Continuously operating the seawater desalination membrane under the conditions of 5ppm of active chlorine, 200ppm of calcium chloride, 200ppm of magnesium sulfate and 32000ppm of sodium chloride, and testing the performance of the membrane at intervals; wherein the pH is 7.0-8, the temperature is 25 ℃, and the test pressure is 5.51MPa. The properties are shown in tables 2 and 3.
TABLE 2 Performance data for diaphragms
TABLE 3 Table 3
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The preparation method of the seawater desalination membrane comprises the following steps:
a) Coating an aqueous phase solution on the polysulfone supporting layer, then coating an oil phase solution, and drying to obtain a nascent reverse osmosis membrane;
b) Sequentially immersing the nascent reverse osmosis membrane into a filling solution, a repairing solution and a glycerol solution, and drying to obtain a sea water desalination membrane;
the filling solution comprises isopropanol, ethyl acetate, water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid;
the repair solution comprises a component a, water and a component b; the component a comprises aliphatic dialdehyde or epoxy compound; the component b comprises tannic acid, nitric acid or hydrochloric acid;
the temperature of the glycerol solution is 60-90 ℃.
2. The preparation method according to claim 1, wherein in the step B), the mass ratio of isopropanol, ethyl acetate, water, polyvinyl alcohol and 1, 5-naphthalene disulfonic acid in the filling solution is 60-80: 0.1-3: 10-30: 0.5-6: 1-4.
3. The production method according to claim 1, wherein in the step B), the aliphatic dialdehydes include at least one of glyoxal, glutaraldehyde, suberaldehyde, 3-oxoglutaraldehyde, and thiodiglycol aldehyde;
the epoxy compound includes at least one of glycidol, diglycidyl ether, glycidyl butyl ether, polyglycidyl ether, epoxy fluoroether, triethylene glycol, butanediol diglycidyl ether, and diglycidyl terephthalate.
4. The preparation method according to claim 1, wherein in the step B), the mass ratio of the component a to the water to the component B is 1 to 10: 85-98.9: 0.1 to 5.
5. The preparation method according to claim 1, wherein in the step B), the mass concentration of the glycerin solution is 2% -10%.
6. The method according to claim 1, wherein in the step B), the nascent reverse osmosis membrane is immersed in the filling solution at a temperature of 25 ℃ for 2 to 5 minutes;
immersing the repairing solution at 25 ℃ for 2-5 min;
the temperature of immersing in the glycerol solution is 60-90 ℃ and the time is 2-5 min.
7. The method of claim 1, wherein in step a), the aqueous solution comprises an amine monomer, a surfactant, a second organic solvent, and water;
the amine monomer comprises at least one of p-phenylenediamine, m-phenylenediamine and 3, 5-diaminobenzoic acid, ethylenediamine, propylenediamine, butylenediamine, pentylene diamine, N- (2-hydroxyethyl) ethylenediamine, hexamethylenediamine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, piperazine and 4-aminomethylpiperazine;
the surfactant comprises at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and sodium stearate;
the second organic solvent comprises N-methyl pyrrolidone;
the mass ratio of the amine monomer to the surfactant to the second organic solvent to the water is 0.5-4: 0.01 to 0.5: 0.5-5: 90.5-98.5;
the temperature of the aqueous phase solution is 10-80 ℃.
8. The method of claim 1, wherein in step a), the oil phase solution comprises an acid chloride monomer and a third organic solvent;
the acyl chloride monomer comprises at least one of phthaloyl chloride, isophthaloyl chloride, biphenylyl dichloride, phthaloyl chloride, trimesoyl chloride, succinyl chloride, ding Sanxian chloride, glutaryl chloride, hexanedioyl chloride, sebacoyl chloride, cyclopropanetriacyl chloride, cyclobutanediacyl chloride, cyclobutanetetracyl chloride, cyclopentanedioyl chloride, cyclopentanetriacyl chloride, cyclopentanetetraacyl chloride, cyclohexanediacyl chloride, cyclohexanetetraacyl chloride, tetrahydrofuranodiacyl chloride and tetrahydrofurantetraacyl chloride;
the third organic solvent is Isopar G;
the mass ratio of the acyl chloride monomer to the third organic solvent is 0.05-0.5: 99.5-99.95;
the coating amount of the oil phase solution is 5-1250 mg/m 2 ；
The temperature of the oil phase solution is 10-80 ℃.
9. The method according to claim 1, wherein in step a), after the oil phase solution is applied, further comprising:
and (5) after standing for 0.2-180 s, removing the redundant oil phase solution.
10. A seawater desalination membrane produced by the production process of any one of claims 1 to 9.
CN202311449171.8A 2023-11-02 2023-11-02 Seawater desalination membrane and preparation method thereof Active CN117181002B (en)

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